CN110139832B - Processing of cobalt sulfate/cobalt dithionate liquors from cobalt resources - Google Patents

Processing of cobalt sulfate/cobalt dithionate liquors from cobalt resources Download PDF

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CN110139832B
CN110139832B CN201780069663.0A CN201780069663A CN110139832B CN 110139832 B CN110139832 B CN 110139832B CN 201780069663 A CN201780069663 A CN 201780069663A CN 110139832 B CN110139832 B CN 110139832B
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lithium
cobalt
sodium
dithionate
sodium sulfate
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CN110139832A (en
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N.乔
J.C-Y.琼格
A.M.纳库
D.D.沃肯廷
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Rocher Manganese Inc
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    • C01D5/00—Sulfates or sulfites of sodium, potassium or alkali metals in general
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    • C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
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Abstract

A process for the removal of water and/or recycling of liquor comprising sodium sulphate and/or sodium dithionate resulting from the processing of a cobalt resource material substantially free of lithium, comprising the steps of: cobalt is precipitated as cobalt carbonate or hydroxide, which is then removed from the liquor, sodium sulfate and sodium dithionate are crystallized and the crystals are removed, after which the crystals are heated to anhydrous sodium sulfate, sulfur dioxide and water, and the anhydrous sodium sulfate is then separated.

Description

Processing of cobalt sulfate/cobalt dithionate liquors from cobalt resources
Prior application
This application is a non-provisional application claiming priority from provisional application No.62/421,139 filed on 11/2016.
Technical Field
The invention relates to the recovery of water and sulphates from liquors (liquor) containing sulphates and dithionates, such as those obtained from hydrometallurgical processing of resource materials containing cobalt, such as positive electrode materials from lithium ion batteries.
Background
It is well known that a reducing agent such as sulfur dioxide can be used in combination with sulfuric acid to leach cobalt from a resource material comprising higher valent cobalt, such as cobalt (III) oxide, to produce cobalt sulfate and cobalt dithionate. This is described in the following reaction:
Co2O3+SO2+H2SO4＝2CoSO4+H2O
Co2O3+2SO2+H2SO4＝2CoS2O6+H2O
cobalt present in the rechargeable lithium ion battery positive electrode material is in a trivalent state and is expected to leach with sulfur dioxide and sulfuric acid. Lithium cobalt oxides such as LiCoO2For common positive electrode materials used in high energy lithium ion batteries typically used in personal electronics, leaching is expected according to the following reaction:
2LiCoO2+SO2+2H2SO4＝Li2SO4+2CoSO4+2H2O
2LiCoO2+3SO2+2H2SO4＝Li2SO4+2CoS2O6+2H2O
2LiCoO2+4SO2+2H2SO4＝Li2S2O6+2CoS2O6+2H2O
experimental work carried out on leaching lithium cobalt oxide with sulphur dioxide and sulphuric acid demonstrated that up to 100% extraction of lithium and cobalt was achieved and dithionate was detected in all leaching tests carried out.
Lithium nickel manganese cobalt oxides such as LiNi0.33Mn0.33Co0.33O2Is an emerging positive electrode material with both high energy and high power suitable for use in electric vehicles, predicted to leach according to the following reaction: 2LiNi0.33Mn0.33Co0.33O2+SO2+2H2SO4＝Li2SO4+2(Ni,Co,Mn)SO4+2H2O2LiNi0.33Mn0.33Co0.33O2+3SO2+2H2SO4＝Li2SO4+2(Ni,Co,Mn)CoS2O6+2H2O2LiNi0.33Mn0.33Co0.33O2+4SO2+2H2SO4＝Li2S2O6+2(Ni,Co,Mn)S2O6+2H2O
(Ni,Co,Mn)SO4And (Ni, Co, Mn) S2O6Respectively, mixed metal sulfates and mixed metal dithionates.
Experimental work carried out on leaching lithium nickel manganese cobalt oxide with sulphur dioxide and sulphuric acid demonstrated that up to 100% extraction of lithium, nickel, manganese and cobalt was achieved and dithionate was detected in all leaching tests carried out.
Lithium nickel cobalt aluminum oxides such as LiNi0.8Co0.15Al0.05O2Is another emerging positive electrode material with both high energy and high power suitable for use in electric vehicles, predicted to leach according to the following reaction: 2LiNi0.8Co0.15Al0.05O2+SO2+2H2SO4＝Li2SO4+2(Ni,Co,Al)SO4+2H2O2LiNi0.8Co0.15Al0.05O2+3SO2+2H2SO4＝Li2SO4+2(Ni,Co,Al)CoS2O6+2H2O2LiNi0.8Co0.15Al0.05O2+4SO2+2H2SO4＝Li2S2O6+2(Ni,Co,Al)S2O6+2H2O
(Ni,Co,Al)SO4And (Ni, Co, Al) S2O6Respectively, mixed metal sulfates and mixed metal dithionates.
Experimental work carried out on leaching lithium nickel manganese cobalt oxide with sulphur dioxide and sulphuric acid demonstrated that up to 100% extraction of lithium, nickel, cobalt and aluminium was achieved and dithionate was detected in all leaching tests carried out.
There is no known prior art method of recovering valuable metals from waste cobalt-containing lithium ion battery positive electrode materials as follows: reductive leaching with sulphur dioxide is used, with simultaneous treatment of dithionate and recovery of water in an energy efficient manner. Although us patent 8,460,631 describes the processing of liquors comprising manganese sulphate and manganese dithionate (which also comprise sodium sulphate and sodium dithionate), it is not obvious from this invention how sodium sulphate and sodium dithionate can be processed together with cobalt sulphate and cobalt dithionate in the presence or absence of lithium sulphate and lithium dithionate. Furthermore, it has been found that a process of treating dithionate and recovering water and recycling the treated solution back to the leach in a closed cycle manner results in significantly improved recovery of lithium (when present).
Disclosure of Invention
Accordingly, one embodiment of the invention is a process for the removal of water and/or recycling from a liquor comprising sodium sulphate and/or sodium dithionate resulting from the processing of a cobalt resource material substantially free of lithium, comprising the steps of: a. cobalt is precipitated wholly or partly as cobalt carbonate, after which it is removed wholly or partly from the liquor, for example by centrifugation or filtration; b. crystallizing sodium sulfate and sodium dithionate to separate a majority of the sodium sulfate and sodium dithionate from the solution; removing the sodium sulfate and sodium dithionate crystals; c. heating the sodium sulfate and sodium dithionate crystals to form anhydrous sodium sulfate, sulfur dioxide, and water (steam); and d, separating the anhydrous sodium sulfate.
Another embodiment of the invention is a process for the dehydration and/or recycling of liquor comprising sodium sulphate and/or sodium dithionate resulting from the processing of cobalt resource material comprising lithium, comprising the steps of; a. precipitating cobalt, in whole or in part, as cobalt carbonate and lithium, in whole or in part, as lithium carbonate, before they are removed, in whole or in part, from the liquor, for example by centrifugation or filtration; b. crystallizing sodium sulfate and sodium dithionate to separate a majority of the sodium sulfate and sodium dithionate from the solution; c. removing the sodium sulfate and sodium dithionate crystals; separating the anhydrous sodium sulfate.
A further embodiment of the invention is a process for the removal of water and/or recycling from a liquor comprising sodium sulphate and/or sodium dithionate resulting from the processing of a cobalt resource material substantially free of lithium, comprising the steps of: a. cobalt is precipitated wholly or partly as cobalt hydroxide, after which it is removed wholly or partly from the liquor, for example by centrifugation or filtration; b. crystallizing sodium sulfate and sodium dithionate to separate a majority of the sodium sulfate and sodium dithionate from the solution; c. removing the sodium sulfate and sodium dithionate crystals; d. heating the sodium sulfate and sodium dithionate crystals to form anhydrous sodium sulfate, sulfur dioxide, and water (steam); separating the anhydrous sodium sulfate.
Yet a further embodiment of the invention is a process for the removal and/or recycling of water from a liquor comprising sodium sulphate and/or sodium dithionate resulting from the processing of a cobalt resource material comprising lithium, comprising the steps of: a. cobalt is precipitated wholly or partly as cobalt hydroxide, after which it is removed wholly or partly from the liquor, for example by centrifugation or filtration; b. precipitating lithium, wholly or partially, from the cobalt hydroxide depleted liquor of 4a as lithium carbonate, after which it is wholly or partially removed from the liquor, for example by centrifugation; c. crystallizing sodium sulfate and sodium dithionate to separate a majority of the sodium sulfate and sodium dithionate from the solution; d. removing the sodium sulfate and sodium dithionate crystals; separating the anhydrous sodium sulfate.
Drawings
Fig. 1-3 illustrate the process flow of the first embodiment of the present invention, wherein "S" represents a solid phase and "L" represents a liquid phase.
Fig. 1 illustrates a process flow for treating waste lithium cobalt oxide according to a first embodiment.
Fig. 2 illustrates a process flow for treating waste lithium nickel manganese cobalt oxide according to a first embodiment.
FIG. 3 illustrates a process flow for treating spent lithium nickel cobalt aluminum oxide according to a first embodiment.
Fig. 4 illustrates a process flow for treating waste lithium cobalt oxide according to a second embodiment.
Fig. 5 illustrates a process flow for treating waste lithium nickel manganese cobalt oxide according to a second embodiment.
FIG. 6 illustrates a process flow for treating spent lithium nickel cobalt aluminum oxide according to a second embodiment.
Fig. 7 illustrates a process flow for treating waste lithium cobalt oxide according to a third embodiment.
Fig. 8 illustrates a process flow for treating waste lithium nickel manganese cobalt oxide according to a third embodiment.
FIG. 9 illustrates a process flow for treating spent lithium nickel cobalt aluminum oxide according to a third embodiment.
Best mode for carrying out the invention
According to the present invention there is provided a hydrometallurgical processing of cobalt (III) oxide containing liquor obtained from sulphurous and sulphuric acid leaching of resource materials containing cobalt (III) oxide, such as those recovered from the positive electrode materials of lithium ion batteries.
For the first embodiment, refer to fig. 1-3.
The liquor comprising cobalt sulfate and cobalt dithionate is treated with sodium carbonate to form cobalt carbonate solids and liquor comprising sodium sulfate and sodium dithionate.
Lithium sulfate and lithium dithionate, if present, were partially precipitated with the cobalt carbonate solids as lithium carbonate solids.
Solids comprising cobalt carbonate and lithium carbonate solids (if present) are removed from the carbonate-treated liquor by filtration or centrifugation.
The solids comprising cobalt carbonate and lithium carbonate solids (if present) are washed to remove soluble impurities and produce a clean material for reuse, for example, for a positive electrode material for a lithium ion battery.
The filtrate or centrate comprising sodium sulfate and sodium dithionate along with residual lithium sulfate and lithium dithionate (if present) is treated with a crystallizer to crystallize a majority of the sodium sulfate and sodium dithionate crystals.
The crystallization can be carried out by cooling to precipitate (crystallize) sodium sulfate decahydrate and sodium dithionate dihydrate or by multiple effect crystallization to precipitate (crystallize) anhydrous sodium sulfate and sodium dithionate.
The sodium sulfate and sodium dithionate crystals are heated to a temperature sufficient to convert the sodium dithionate crystals to sodium sulfate and to recycle sulfur dioxide and water for leaching the cobalt resource material. The temperatures used for the conversion of sodium dithionate into sodium sulfate and sulfur dioxide are described by Chow et al (New Developments in the Recovery of mineral from Low-grade resources ", Minerals & Metallurgical Processing, Vol.29, No. 1, month 2 2012, pages 70-71).
Most of the sodium sulphate and sodium dithionate are removed and the crystallizer liquor containing lithium sulphate and lithium dithionate (if lithium is present in the resource material) is recycled to the leaching circuit for further recovery of lithium and cobalt not previously recovered and reuse of water in an energy efficient manner.
Alternatively, most of the sodium sulfate and sodium dithionate may be removed and a portion of the crystallizer liquor comprising lithium sulfate and lithium dithionate (if lithium is present in the resource material) may be passed through a nanofiltration membrane to produce: water-rich sulphate-and dithionate-free liquor, which is exported for recycling; and sodium sulfate and sodium dithionate concentrates along with lithium sulfate and lithium dithionate for recycle to the sodium sulfate and sodium dithionate crystallizers.
The precipitated cobalt and lithium containing compounds are useful in the manufacture of positive electrode materials for lithium ion batteries. This is done by: the desired ratio of compounds comprising cobalt and lithium is combined and the mixture is subjected to a heat treatment procedure. Jones et al ("Li)xCoO2(0<x.ltoreq.1) A New Material for batteries of High Energy Density, Solid State Ionics, 3/4, 1981, pp 171-174) describes the manufacture of lithium cobalt oxide Cathode materials by treating lithium and cobalt compoundsA method. Lu et al ("U.S. patent No.8,685,565", 4 months 2014) describe a process for the manufacture of lithium nickel manganese cobalt oxides by treating lithium, nickel, manganese and cobalt compounds. Kim et al "(Synthesis of High-sensitivity Nickel Cobalt Aluminum Hydroxide by Continuous prediction Method", ACS Applied Materials&Interfaces, 4, 2012, pages 586-589) describe a process for producing lithium nickel cobalt aluminum oxide by treating lithium, nickel, cobalt and aluminum compounds. Commercial battery manufacturers typically develop and use their own proprietary processing methods to manufacture positive electrode materials for lithium ion batteries.
The conversion of cobalt sulfate and cobalt dithionate to sodium sulfate and sodium dithionate provides a novel method of treating dithionate, increasing lithium recovery, and recycling water in an energy efficient manner.
For the second embodiment, refer to FIGS. 4 to 6
Treating liquor comprising cobalt sulfate and cobalt dithionate with sodium hydroxide to form cobalt hydroxide solids and liquor comprising sodium sulfate and sodium dithionate;
removing solids comprising cobalt hydroxide from the hydroxide-treated liquor by filtration or centrifugation;
washing the solids comprising cobalt hydroxide to remove soluble impurities and produce a clean material for reuse, for example, as a positive electrode material for a lithium ion battery;
the addition of sodium carbonate to the remaining solution causes a portion of the lithium (if present) to precipitate as lithium carbonate;
removing the lithium carbonate solids from the carbonate-treated liquor by filtration or centrifugation;
washing the lithium carbonate solids to remove soluble impurities and produce a clean material for reuse, for example, as a positive electrode material for a lithium ion battery;
treating the filtrate or centrate comprising sodium sulfate and sodium dithionate together with residual lithium sulfate and lithium dithionate (if present) with a crystallizer to crystallize a majority of the sodium sulfate and sodium dithionate crystals;
crystallization can be carried out by cooling to precipitate (crystallize) sodium sulfate decahydrate and sodium dithionate dihydrate or by multiple-effect crystallization to precipitate (crystallize) anhydrous sodium sulfate and sodium dithionate;
heating the sodium sulfate and sodium dithionate crystals to a temperature sufficient to convert the sodium dithionate crystals to sodium sulfate and to recycle sulfur dioxide and water for leaching the cobalt resource material;
most of the sodium sulphate and sodium dithionate are removed and the crystallizer liquor containing lithium sulphate and lithium dithionate (if lithium is present in the resource material) is recycled to the leaching circuit for further recovery of lithium and cobalt not previously recovered and reuse of water in an energy efficient manner.
Alternatively, a majority of the sodium sulfate and sodium dithionate may be removed and a majority of the crystallizer liquor comprising lithium sulfate and lithium dithionate (if lithium is present in the resource material) passed through a nanofiltration membrane to produce: water-rich sulphate-and dithionate-free liquor, which is exported for recycling; and sodium sulfate and sodium dithionate concentrates along with lithium sulfate and lithium dithionate (if lithium is present in the resource material) for recycle to the sodium sulfate and sodium dithionate crystallizers.
For embodiment three, refer to fig. 7-9.
Treating liquor comprising cobalt sulfate and cobalt dithionate with lithium hydroxide to form cobalt hydroxide solids and liquor comprising lithium sulfate and lithium dithionate;
the lithium hydroxide may be generated by processing lithium carbonate recovered by previous operations of the flow scheme. Wietelmann et al ("Lithium and Lithium Compounds", Ullmann's Encyclopedia of Industrial Chemistry, Wiley-VCH Verlag GmbH & Co, 2013, page 24) describe a process for producing Lithium hydroxide by reacting Lithium carbonate with calcium hydroxide;
removing solids comprising cobalt hydroxide from the hydroxide-treated liquor by filtration or centrifugation;
washing the solids comprising cobalt hydroxide to remove soluble impurities and produce a clean material for reuse, for example, as a positive electrode material for a lithium ion battery;
the addition of sodium carbonate to the remaining solution causes a portion of the lithium (if present) to precipitate as lithium carbonate;
removing the lithium carbonate solids from the carbonate-treated liquor by filtration or centrifugation;
washing the lithium carbonate solids to remove soluble impurities and produce a clean material for reuse, for example, as a positive electrode material for a lithium ion battery;
treating the filtrate or centrate comprising sodium sulfate and sodium dithionate together with residual lithium sulfate and lithium dithionate (if present) with a crystallizer to crystallize a majority of the sodium sulfate and sodium dithionate crystals;
crystallization can be carried out by cooling to precipitate (crystallize) sodium sulfate decahydrate and sodium dithionate dihydrate or by multiple-effect crystallization to precipitate (crystallize) anhydrous sodium sulfate and sodium dithionate;
heating the sodium sulfate and sodium dithionate crystals to a temperature sufficient to convert the sodium dithionate crystals to sodium sulfate and to recycle sulfur dioxide and water for leaching the cobalt resource material;
most of the sodium sulphate and sodium dithionate are removed and the crystallizer liquor containing lithium sulphate and lithium dithionate (if lithium is present in the resource material) is recycled to the leaching circuit for further recovery of lithium and cobalt not previously recovered and reuse of water in an energy efficient manner.
Alternatively, most of the sodium sulfate and sodium dithionate may be removed and a portion of the crystallizer liquor comprising lithium sulfate and lithium dithionate may be passed through a nanofiltration membrane to produce: water-rich sulphate-and dithionate-free liquor, which is exported for recycling; and sodium sulfate and sodium dithionate concentrates along with lithium sulfate and lithium dithionate for recycle to the sodium sulfate and sodium dithionate crystallizers.
The precipitated cobalt and lithium containing compounds are useful in the manufacture of positive electrode materials for lithium ion batteries.
For the first embodiment shown in fig. 1 for treating lithium cobalt oxide, the flow is described as follows:
in the leaching reactor (12), LiCoO having the chemical formula2The waste lithium ion battery anode material and SO2And H2SO4Reagents and solutions comprising water and possibly lithium and/or cobalt that have not been previously recovered from the final stages of the process are combined and mixed. Lithium and cobalt are dissolved in the solution, producing a leach solution comprising cobalt sulfate, cobalt dithionate, lithium sulfate, and lithium dithionate.
Transferring the leach solution to a precipitation reactor (20), adding a sodium carbonate solution in the precipitation reactor (20) and mixing to precipitate cobalt and a portion of the dissolved lithium as cobalt carbonate and lithium carbonate solids and form a solution comprising primarily lithium sulfate, lithium dithionate, sodium sulfate, and sodium dithionate.
The precipitation reaction takes place as follows:
CoSO4+Na2CO3＝CoCO3+Na2SO4near complete conversion
CoS2O6+Na2CO3＝CoCO3+Na2S2O6Near complete conversion
Li2SO4+Na2CO3＝Li2CO3+Na2SO4Partial transformation
Li2S2O6+Na2CO3＝Li2CO3+Na2S2O6Partial transformation
The slurry comprising the solid mixture and the liquid is filtered (14) to separate lithium carbonate and cobalt carbonate, which are washed to produce a collected product (16).
The filtrate is transferred to a crystallizer (18), in which crystallizer (18) part of the sodium sulphate and sodium dithionate is crystallized as solid crystals by multiple effect crystallization or cooling crystallization. Solid sodium sulfate and sodium dithionate crystals are collected from the solution using a centrifuge or filter (22). Heating the sodium sulfate and sodium dithionate crystals to about 120 deg.C (24 deg.C) to effect crystallizationDecomposition of sodium disulfate to sodium sulfate by-product and SO2，SO2Can be recycled back to leaching. The mother liquor (mother liquor) contains the remaining lithium sulfate, lithium dithionate, sodium sulfate, sodium dithionate and water, and is recycled (26) back to the leach to minimize water consumption and maximize lithium recovery throughout the process. Alternatively, a portion of the mother liquor may be treated by nanofiltration (28) to produce clean water (30) which is used to wash the product and to recycle the spent wash water (32) back to the leach. The concentrate (34) from nanofiltration is recycled back to the crystallizer to maximize sodium sulfate recovery. The combined lithium carbonate and cobalt carbonate collection product (16) is heat treated (36) to produce a new positive electrode compound for use in a lithium ion battery. If desired, additional lithium carbonate and or cobalt carbonate may be added to the collected product to achieve the desired ratio of lithium to cobalt prior to heat treatment.
For the first embodiment shown in fig. 2 for processing lithium nickel manganese cobalt oxide, the flow is described as follows:
in a leaching reactor (40), a spent lithium nickel manganese cobalt oxide cathode material (e.g., LiNi of the formula)0.33Mn0.33Co0.33O2) With SO2And H2SO4Reagents and solutions comprising water and possibly lithium and/or nickel and/or manganese and/or cobalt that have not been previously recovered from the final stages of the process are combined and mixed. Lithium, nickel, manganese and cobalt are dissolved in the solution, producing a leach solution comprising nickel manganese cobalt sulphate, nickel manganese cobalt dithionate, lithium sulphate and lithium dithionate.
The leach solution is transferred to a precipitation reactor (48), where sodium carbonate is added and mixed to precipitate nickel, manganese and cobalt and part of the dissolved lithium as nickel, manganese, cobalt and lithium carbonate solids and form a solution comprising mainly lithium sulfate, lithium dithionate, sodium sulfate and sodium dithionate.
The precipitation reaction takes place as follows:
(Ni,Mn,Co)SO4+Na2CO3＝(Ni,Mn,Co)CO3+Na2SO4near complete conversion
(Ni,Mn,Co)S2O6+Na2CO3＝(Ni,Mn,Co)CO3+Na2S2O6Near complete conversion
Li2SO4+Na2CO3＝Li2CO3+Na2SO4Partial transformation
Li2S2O6+Na2CO3＝Li2CO3+Na2S2O6Partial transformation
The slurry comprising the solid mixture and liquid is filtered (42) to separate lithium carbonate and nickel manganese cobalt carbonate, which are washed to produce a collected product (44).
The filtrate is transferred to a crystallizer (46), in which crystallizer (46) part of the sodium sulphate and sodium dithionate is crystallized as solid crystals by multiple effect crystallization or cooling crystallization. Solid sodium sulfate and sodium dithionate crystals are collected from the solution using a centrifuge or filter (50). Heating the sodium sulfate and sodium dithionate crystals to about 120 deg.C (52) decomposes the sodium dithionate into sodium sulfate by-product and SO2，SO2May be recycled to leaching. The mother liquor, which contains the remaining lithium sulfate, lithium dithionate, sodium sulfate, sodium dithionate and water, is recycled (54) back to the leach to minimize water consumption and maximize lithium recovery throughout the process. Alternatively, a portion of the mother liquor may be treated by nanofiltration (56) to produce clean water (58) which is used to wash the product and to recycle the spent wash water (60) back to the leach. The concentrate (62) from nanofiltration is recycled back to the crystallizer to maximize sodium sulfate recovery. The combined lithium carbonate and nickel manganese cobalt carbonate collection product (44) is heat treated (64) to produce a new positive electrode compound for use in a lithium ion battery. If desired, additional lithium, nickel, manganese and or cobalt compounds may be added to the collected product to achieve the desired ratio of lithium, nickel, manganese and cobalt prior to heat treatment.
For the first embodiment shown in fig. 3 for treating lithium nickel cobalt aluminum oxide, the flow is described as follows:
in the leaching processIn the reactor (70), the spent lithium nickel cobalt aluminum oxide cathode material (e.g., LiNi of the formula)0.8Co0.15Al0.05O2) With SO2And H2SO4Reagents and solutions comprising water and possibly lithium and/or nickel and/or cobalt and/or aluminum that have not been previously recovered from the final stages of the process are combined and mixed. Lithium, nickel, cobalt and aluminum are dissolved in solution, producing a leach solution comprising nickel cobalt aluminum sulfate, nickel cobalt aluminum dithionate, lithium sulfate and lithium dithionate.
Transferring the leach solution to a precipitation reactor (78), adding sodium carbonate in the precipitation reactor (78) and mixing to precipitate nickel, cobalt and aluminum and a portion of the dissolved lithium as nickel, cobalt, aluminum and lithium carbonate solids and form a solution comprising primarily lithium sulfate, lithium dithionate, sodium sulfate and sodium dithionate.
The precipitation reaction takes place as follows:
(Ni,Co,Al)SO4+Na2CO3＝(Ni,Co,Al)CO3+Na2SO4near complete conversion
(Ni,Co,Al)S2O6+Na2CO3＝(Ni,Co,Al)CO3+Na2S2O6Near complete conversion
Li2SO4+Na2CO3＝Li2CO3+Na2SO4Partial transformation
Li2S2O6+Na2CO3＝Li2CO3+Na2S2O6Partial transformation
The slurry comprising the solid mixture and the liquid is filtered (72) to separate lithium carbonate and nickel cobalt aluminum carbonate, which are washed to produce a collected product (74).
The filtrate is transferred to a crystallizer (76), in which crystallizer (76) part of the sodium sulphate and sodium dithionate is crystallized as solid crystals by multiple effect crystallization or cooling crystallization. Collecting solid sodium sulfate and sodium dithionate crystals from the solution with a centrifuge or filter (80). Heating the sodium sulfate and sodium dithionate crystals to about 120 deg.C (82) decomposes the sodium dithionate into sodium sulfate by-product and SO2，SO2May be recycled to leaching. The mother liquor, which contains the remaining lithium sulfate, lithium dithionate, sodium sulfate, sodium dithionate and water, is recycled (84) back to the leach to minimize water consumption and maximize lithium recovery throughout the process. Alternatively, a portion of the mother liquor may be treated by nanofiltration (86) to produce clean water (88) which is used to wash the product and to recycle the spent wash water (90) back to the leach. The concentrate from nanofiltration (92) is recycled back to the crystallizer to maximize sodium sulfate recovery. The combined lithium carbonate and nickel cobalt aluminum carbonate collection product (74) is heat treated (94) to produce a new positive electrode compound for use in a lithium ion battery. If desired, additional lithium, nickel, cobalt and or aluminum compounds may be added to the collected product to achieve the desired ratio of lithium, nickel, cobalt and aluminum prior to heat treatment.
For the second embodiment shown in fig. 4 for treating lithium cobalt oxide, the flow is described as follows:
in an extraction reactor (100), LiCoO having the chemical formula2The waste lithium ion battery anode material and SO2And H2SO4Reagents and solutions comprising water and possibly lithium and/or cobalt that have not been previously recovered from the final stages of the process are combined and mixed. Lithium and cobalt are dissolved in the solution, producing a leach solution comprising cobalt sulfate, cobalt dithionate, lithium sulfate, and lithium dithionate.
Transferring the leach solution to a precipitation reactor (108), adding sodium hydroxide in the precipitation reactor (108) and mixing to selectively precipitate cobalt as cobalt hydroxide and form a solution comprising primarily lithium sulfate, lithium dithionate, sodium sulfate, and sodium dithionate.
The precipitation reaction takes place as follows:
CoSO4+2NaOH＝Co(OH)2+Na2SO4near complete conversion
CoS2O6+2NaOH＝Co(OH)2+Na2S2O6Near complete conversion
The slurry comprising the solid mixture and liquid is filtered (102) to separate cobalt hydroxide, which is washed to produce a collected product (104).
The filtered solution is transferred to a second precipitation reactor (106), sodium carbonate is added in the second precipitation reactor (106) and mixed to precipitate part of the dissolved lithium as lithium carbonate solids and form a solution comprising mainly lithium sulfate, lithium dithionate, sodium sulfate and sodium dithionate.
The slurry comprising the solid mixture and the liquid is filtered (118) to isolate lithium carbonate, which is washed to produce a collected product (120).
The filtrate is transferred to a crystallizer (114), in which crystallizer (114) part of the sodium sulphate and sodium dithionate is crystallized as solid crystals by multiple effect crystallization or cooling crystallization. Solid sodium sulfate and sodium dithionate crystals are collected from the solution with a centrifuge or filter (116). Heating the sodium sulfate and sodium dithionate crystals to about 120 deg.C (110) decomposes the sodium dithionate into sodium sulfate by-product and SO2，SO2May be recycled to leaching. The mother liquor, comprising the remaining lithium sulfate, lithium dithionate, sodium sulfate, sodium dithionate and water, is recycled (112) back to the leach to minimize water consumption and maximize lithium recovery throughout the process. Alternatively, a portion of the mother liquor may be treated by nanofiltration (122) to produce clean water (124) which is used to wash the product and to recycle the spent wash water (126, 128) back to the leach. The concentrate (130) from nanofiltration is recycled back to the crystallizer to maximize sodium sulfate recovery. The lithium carbonate (120) and cobalt hydroxide (104) collected products are mixed to the desired ratio of lithium and cobalt and heat treated (132) to make new positive electrode compounds for use in lithium ion batteries. If desired, additional lithium and or cobalt compounds may be added to the collected product to achieve the desired ratio of lithium to cobalt prior to heat treatment.
For the second embodiment shown in fig. 5 for processing lithium nickel manganese cobalt oxide, the flow is described as follows:
in the leaching reactor (140), waste lithium nickel manganese cobalt oxideCathode material (e.g. LiNi of formula)0.33Mn0.33Co0.33O2) With SO2And H2SO4Reagents and solutions comprising water and possibly lithium and/or nickel and/or manganese and/or cobalt that have not been previously recovered from the final stages of the process are combined and mixed. Lithium, nickel, manganese and cobalt are dissolved in the solution, producing a leach solution comprising nickel manganese cobalt sulphate, nickel manganese cobalt dithionate, lithium sulphate and lithium dithionate.
Transferring the leach solution to a precipitation reactor (148), adding sodium hydroxide and mixing in the precipitation reactor (148) to selectively precipitate nickel, manganese, and cobalt as nickel manganese cobalt hydroxide and form a solution comprising primarily lithium sulfate, lithium dithionate, sodium sulfate, and sodium dithionate.
The precipitation reaction takes place as follows:
(Ni,Mn,Co)SO4+2NaOH＝(Ni,Mn,Co)(OH)2+Na2SO4near complete conversion
(Ni,Mn,Co)S2O6+2NaOH＝(Ni,Mn,Co)(OH)2+Na2S2O6Near complete conversion
The slurry comprising the solid mixture and liquid is filtered (142) to separate nickel manganese cobalt hydroxide, which is washed to produce a collected product (144).
The filtered solution is transferred to a second precipitation reactor (146), sodium carbonate is added in the second precipitation reactor (146) and mixed to precipitate part of the dissolved lithium as lithium carbonate solids and form a solution comprising mainly lithium sulfate, lithium dithionate, sodium sulfate and sodium dithionate.
The slurry comprising the solid mixture and the liquid is filtered (158) to isolate lithium carbonate, which is washed to produce a collected product (160).
The filtrate is transferred to a crystallizer (154), in which crystallizer (154) part of the sodium sulphate and sodium dithionate is crystallized as solid crystals by multiple effect crystallization or cooling crystallization. Solid sodium sulfate and sodium dithionate crystals are collected from the solution with a centrifuge or filter (156). Sodium sulfate and dithioHeating the sodium salt crystals to about 120 deg.C (150 deg.C) decomposes sodium dithionate into sodium sulfate by-product and SO2，SO2May be recycled to leaching. The mother liquor, which contains the remaining lithium sulfate, lithium dithionate, sodium sulfate, sodium dithionate and water, is recycled (152) back to the leach to minimize water consumption and maximize lithium recovery throughout the process. Alternatively, a portion of the mother liquor may be treated by nanofiltration (162) to produce clean water (164) which is used to wash the product and to recycle the spent wash water (166, 168) back to the leach. The concentrate (170) from nanofiltration is recycled back to the crystallizer to maximize sodium sulfate recovery. The lithium carbonate (160) and nickel manganese cobalt hydroxide (144) collected products are mixed to the desired ratio of lithium, nickel, manganese and cobalt and heat treated (172) to make new positive electrode compounds for use in lithium ion batteries. If desired, additional lithium, nickel, manganese and or cobalt compounds may be added to the collected product to achieve the desired ratio of lithium, nickel, manganese and cobalt prior to heat treatment.
For the second embodiment shown in fig. 6 for treating lithium nickel cobalt aluminum oxide, the flow is described as follows:
in an extraction reactor (180), spent lithium nickel cobalt aluminum oxide cathode material (e.g., LiNi of the formula)0.8Co0.15Al0.05O2) With SO2And H2SO4Reagents and solutions comprising water and possibly lithium and/or nickel and/or cobalt and/or aluminum that have not been previously recovered from the final stages of the process are combined and mixed. Lithium, nickel, cobalt and aluminum are dissolved in solution, producing a leach solution comprising nickel cobalt aluminum sulfate, nickel cobalt aluminum dithionate, lithium sulfate and lithium dithionate.
The leach solution is transferred to a precipitation reactor (188), sodium hydroxide is added and mixed in the precipitation reactor (188) to selectively precipitate nickel, cobalt, and aluminum as nickel cobalt aluminum hydroxide and form a solution comprising primarily lithium sulfate, lithium dithionate, sodium sulfate, and sodium dithionate.
The precipitation reaction takes place as follows:
(Ni,Co,Al)SO4+2NaOH＝(Ni,Co,Al)(OH)2+Na2SO4near complete conversion
(Ni,Co,Al)S2O6+2NaOH＝(Ni,Co,Al)(OH)2+Na2S2O6Near complete conversion
The slurry comprising the solid mixture and liquid is filtered (182) to separate the nickel cobalt aluminum hydroxide, which is washed to produce a collected product (184).
The filtered solution is transferred to a second precipitation reactor (186), sodium carbonate is added in the second precipitation reactor (186) and mixed to precipitate a portion of the dissolved lithium as lithium carbonate solids and form a solution comprising primarily lithium sulfate, lithium dithionate, sodium sulfate, and sodium dithionate.
The slurry comprising the solid mixture and liquid is filtered (198) to separate lithium carbonate, which is washed to produce a collected product (200).
The filtrate is transferred to a crystallizer (194), and part of the sodium sulfate and sodium dithionate in the crystallizer (194) is crystallized into solid crystals by multiple-effect crystallization or cooling crystallization. Solid sodium sulfate and sodium dithionate crystals are collected from the solution using a centrifuge or filter (196). Heating the sodium sulfate and sodium dithionate crystals to about 120 deg.C (190 deg.C) decomposes the sodium dithionate into sodium sulfate by-product and SO2，SO2May be recycled to leaching. The mother liquor, which contains the remaining lithium sulfate, lithium dithionate, sodium sulfate, sodium dithionate and water, is recycled (192) back to the leach to minimize water consumption and maximize lithium recovery throughout the process. Alternatively, a portion of the mother liquor may be treated by nanofiltration (202) to produce clean water (204) which is used to wash the product and to recycle the spent wash water (206, 208) back to the leach. The concentrate (210) from nanofiltration is recycled back to the crystallizer to maximize sodium sulfate recovery. The lithium carbonate (200) and nickel cobalt aluminum hydroxide (184) collected products are mixed to the desired ratio of lithium, nickel, cobalt and aluminum and heat treated (212) to make new positive electrode compounds for use in lithium ion batteries. If desired, additional lithium, nickel, cobalt and or aluminum compounds may be added to the collected product to achieve lithium, cobalt and or aluminum concentration prior to heat treatment,Desired ratios of nickel, cobalt and aluminum.
For embodiment three shown in fig. 7 for treating lithium cobalt oxide, the flow is described as follows:
in the leaching reactor (220), LiCoO having the chemical formula2The waste lithium ion battery anode material and SO2And H2SO4Reagents and solutions comprising water and possibly lithium and/or cobalt that have not been previously recovered from the final stages of the process are combined and mixed. Lithium and cobalt are dissolved in the solution, producing a leach solution comprising cobalt sulfate, cobalt dithionate, lithium sulfate, and lithium dithionate.
Transferring the leach solution to a precipitation reactor (228), adding lithium hydroxide in the precipitation reactor (228) and mixing to selectively precipitate cobalt as cobalt hydroxide and form a solution comprising primarily lithium sulfate and lithium dithionate.
The precipitation reaction takes place as follows:
CoSO4+2LiOH＝Co(OH)2+Li2SO4near complete conversion
CoS2O6+2LiOH＝Co(OH)2+Li2S2O6Near complete conversion
The slurry comprising the solid mixture and liquid is filtered (222) to separate cobalt hydroxide, which is washed to produce a collected product (224).
The filtered solution is transferred to a second precipitation reactor (226), sodium carbonate is added in the second precipitation reactor (226) and mixed to precipitate part of the dissolved lithium as lithium carbonate solids and form a solution comprising mainly lithium sulfate, lithium dithionate, sodium sulfate and sodium dithionate.
The slurry comprising the solid mixture and the liquid is filtered (238) to isolate lithium carbonate, which is washed (240). A portion of the lithium carbonate is collected as product (242). The other portion of the lithium carbonate is further mixed (244) with calcium hydroxide to produce a slurry comprising dissolved lithium hydroxide and solid calcium carbonate. The slurry is filtered (246) to separate calcium carbonate solids and lithium hydroxide solution, which is reused to precipitate the cobalt compound (228).
The filtrate from the second filter (238) is transferred to a crystallizer (234), where part of the sodium sulphate and sodium dithionate is crystallized as solid crystals by multiple effect crystallization or cooling crystallization. Solid sodium sulfate and sodium dithionate crystals are collected from the solution with a centrifuge or filter (236). Heating the sodium sulfate and sodium dithionate crystals to about 120 deg.C (230 deg.C) to decompose sodium dithionate into sodium sulfate by-product and SO2，SO2May be recycled to leaching. The mother liquor, comprising the remaining lithium sulfate, lithium dithionate, sodium sulfate, sodium dithionate and water, is recycled (232) back to the leach to minimize water consumption and maximize lithium recovery throughout the process. Alternatively, a portion of the mother liquor may be treated by nanofiltration (248) to produce clean water (250) which is used to wash the product and to recycle the spent wash water (252, 254) back to the leach. The concentrate (256) from nanofiltration is recycled back to the crystallizer to maximize sodium sulfate recovery. The lithium carbonate (242) and cobalt hydroxide (224) collected products are mixed to the desired ratio of lithium and cobalt and heat treated (258) to make new positive electrode compounds for use in lithium ion batteries. If desired, additional lithium and or cobalt compounds may be added to the collected product to achieve the desired ratio of lithium to cobalt prior to heat treatment.
For the third embodiment for processing lithium nickel manganese cobalt oxide shown in fig. 8, the flow is described as follows:
in the leaching reactor (270), a spent lithium nickel manganese cobalt oxide cathode material (e.g., LiNi of the formula)0.33Mn0.33Co0.33O2) With SO2And H2SO4Reagents and solutions comprising water and possibly lithium and/or nickel and/or manganese and/or cobalt that have not been previously recovered from the final stages of the process are combined and mixed. Lithium, nickel, manganese and cobalt are dissolved in the solution, producing a leach solution comprising nickel manganese cobalt sulphate, nickel manganese cobalt dithionate, lithium sulphate and lithium dithionate.
Transferring the leach solution to a precipitation reactor (278), adding lithium hydroxide and mixing in the precipitation reactor (278) to selectively precipitate nickel, manganese, and cobalt as nickel manganese cobalt hydroxide and form a solution comprising primarily lithium sulfate and lithium dithionate.
The precipitation reaction takes place as follows:
(Ni,Mn,Co)SO4+2LiOH＝(Ni,Mn,Co)(OH)2+Li2SO4near complete conversion
(Ni,Mn,Co)S2O6+2LiOH＝(Ni,Mn,Co)(OH)2+Li2S2O6Near complete conversion
The slurry comprising the solid mixture and liquid is filtered (272) to separate nickel manganese cobalt hydroxide, which is washed to produce a collected product (274).
The filtered solution is transferred to a second precipitation reactor (276), sodium carbonate is added in the second precipitation reactor (276) and mixed to precipitate part of the dissolved lithium as lithium carbonate solids and form a solution comprising mainly lithium sulfate, lithium dithionate, sodium sulfate and sodium dithionate.
The slurry comprising the solid mixture and the liquid is filtered (288) to isolate lithium carbonate, which is washed (290). A portion of the lithium carbonate was collected as product (292). The other portion of the lithium carbonate is further mixed (294) with calcium hydroxide to produce a slurry comprising dissolved lithium hydroxide and solid calcium carbonate. The slurry is filtered (296) to separate calcium carbonate solids and lithium hydroxide solution, which is reused to precipitate cobalt compounds (278).
The filtrate from the second filter (288) is transferred to a crystallizer (284), where part of the sodium sulphate and sodium dithionate is crystallized as solid crystals by multiple effect crystallization or cooling crystallization. Solid sodium sulfate and sodium dithionate crystals are collected from the solution with a centrifuge or filter (286). Heating the sodium sulfate and sodium dithionate crystals to about 120 deg.C (280 deg.C) to decompose sodium dithionate into sodium sulfate by-product and SO2，SO2May be recycled to leaching. The mother liquor, comprising the remaining lithium sulfate, lithium dithionate, sodium sulfate, sodium dithionate and water, is recycled (282) back to the leach to consume waterMinimizing and maximizing lithium recovery throughout the process. Alternatively, a portion of the mother liquor may be treated by nanofiltration (298) to produce clean water (300) which is used to wash the products and to recycle the spent wash water (302, 304) back to the leach. The concentrate (306) from nanofiltration is recycled back to the crystallizer to maximize sodium sulfate recovery. The lithium carbonate (292) and nickel manganese cobalt hydroxide (274) collected products are mixed to the desired ratio of lithium, nickel, manganese and cobalt and heat treated (308) to make new positive electrode compounds for use in lithium ion batteries. If desired, additional lithium, nickel, manganese and or cobalt compounds may be added to the collected product to achieve the desired ratio of lithium, nickel, manganese and cobalt prior to heat treatment.
For the third embodiment shown in fig. 9 for treating lithium nickel cobalt aluminum oxide, the flow is described as follows:
in the leaching reactor (320), spent lithium nickel cobalt aluminum oxide cathode material (e.g., LiNi of the formula)0.8Co0.15Al0.05O2) With SO2And H2SO4Reagents and solutions comprising water and possibly lithium and/or nickel and/or cobalt and/or aluminum that have not been previously recovered from the final stages of the process are combined and mixed. Lithium, nickel, cobalt and aluminum are dissolved in solution, producing a leach solution comprising nickel cobalt aluminum sulfate, nickel cobalt aluminum dithionate, lithium sulfate and lithium dithionate.
Transferring the leach solution to a precipitation reactor (328), adding lithium hydroxide in the precipitation reactor (328) and mixing to selectively precipitate nickel, cobalt and aluminum as nickel cobalt aluminum hydroxide and form a solution comprising primarily lithium sulfate and lithium dithionate.
The precipitation reaction takes place as follows:
(Ni,Co,Al)SO4+2LiOH＝(Ni,Co,Al)(OH)2+Li2SO4near complete conversion
(Ni,Co,Al)S2O6+2LiOH＝(Ni,Co,Al)(OH)2+Li2S2O6Near complete conversion
The slurry comprising the solid mixture and liquid is filtered (322) to separate the nickel cobalt aluminum hydroxide, which is washed to produce a collected product (324).
The filtered solution is transferred to a second precipitation reactor (326), sodium carbonate is added in the second precipitation reactor (326) and mixed to precipitate part of the dissolved lithium as lithium carbonate solids and form a solution comprising mainly lithium sulfate, lithium dithionate, sodium sulfate and sodium dithionate.
The slurry comprising the solid mixture and the liquid is filtered (338) to isolate lithium carbonate, which is washed (340). A portion of the lithium carbonate was collected as product (342). The other portion of the lithium carbonate is further mixed (344) with calcium hydroxide to produce a slurry comprising dissolved lithium hydroxide and solid calcium carbonate. The slurry is filtered (346) to separate calcium carbonate solids and lithium hydroxide solution, which is reused to precipitate nickel, cobalt and aluminum compounds (328).
The filtrate from the second filter (338) is transferred to a crystallizer (334), where part of the sodium sulphate and sodium dithionate is crystallized as solid crystals by multiple effect crystallization or cooling crystallization. Solid sodium sulfate and sodium dithionate crystals are collected from the solution with a centrifuge or filter (336). Heating the sodium sulfate and sodium dithionate crystals to about 120 deg.C (330) decomposes the sodium dithionate into sodium sulfate by-product and SO2，SO2May be recycled to leaching. The mother liquor, comprising the remaining lithium sulfate, lithium dithionate, sodium sulfate, sodium dithionate and water, is recycled (332) back to the leach to minimize water consumption and maximize lithium recovery throughout the process. Alternatively, a portion of the mother liquor may be treated by nanofiltration (348) to produce clean water (350) which is used to wash the product and to recycle the spent wash water (352, 354) back to the leach. The concentrate (356) from nanofiltration is recycled back to the crystallizer to maximize sodium sulfate recovery. The lithium carbonate (342) and nickel cobalt aluminum hydroxide (324) collected products are mixed to the desired ratio of lithium, nickel, cobalt and aluminum and heat treated (358) to make new positive electrode compounds for use in lithium ion batteries. If desired, additional lithium, nickel, cobalt and or aluminum compounds may be added to the collected product to thermally treatThe desired ratios of lithium, nickel, cobalt and aluminum were achieved prior to treatment.
The examples illustrate the invention:
1. lithium cobalt oxide was leached with sulfur dioxide and sulfuric acid (run # LT4)
Will be represented by the chemical formula LiCoO2The structured lithium cobalt oxide (Alfa Aesar) was used for this experimental work. Leaching is carried out by: 25 g LiCoO2Mixed with 250mL of 2 mol/l sulfuric acid. Sulfur dioxide gas is continuously bubbled into the leach solution to maintain an oxidation-reduction potential (ORP) of ≦ 400 mV. The leaching vessel consisted of a three-necked round bottom flask and was stirred with a magnetic stir bar. One port of the flask was used to monitor ORP, a condenser was added to the other port to condense the vapor back into the vessel and another port was used to measure temperature. The experiments were performed without temperature control. The leach was determined to be exothermic as the temperature rose to as high as 71 ℃ after 5 minutes of leaching and further cooled to 21C after 120 minutes of experimentation. Inductively coupled plasma spectroscopy (ICP) analysis of the solution showed that 100% of the lithium and cobalt were extracted after 5 minutes of leaching.
2. Lithium cobalt oxide was leached with pyrosulfite and sulfuric acid (run # LT6)
Leaching is carried out by: 12.5 grams LiCoO2Mixed with 250mL of 2 mol/l sulfuric acid and 0.67 mol/l sodium metabisulfite. The leaching vessel consisted of a three-necked round bottom flask and was stirred with a magnetic stir bar. One port of the flask was used to monitor ORP, a condenser was added to the other port to condense the vapor back into the vessel and another port was used to measure temperature. The experiments were performed without temperature control. The leach was determined to be exothermic as the temperature rose to as high as 60 ℃ after 5 minutes of leaching and was further cooled to 25 ℃ after 120 minutes of experimentation. ICP analysis of the solution showed that 100% of the lithium and cobalt were extracted after 5 minutes of leaching.
3. Cobalt and lithium were precipitated as cobalt carbonate and lithium carbonate (run # PTCL1)
A200 mL solution containing 5.59g/L lithium and 50.01g/L cobalt, pH 1.59, was prepared by: the lithium cobalt oxide is leached with sulfur dioxide in combination with sulfuric acid. The precipitation test was performed by: 31.83 grams of anhydrous sodium carbonate (calculated as 1.2 times the stoichiometric amount of sodium carbonate required to precipitate all of the lithium and cobalt as carbonate) was added. Thereafter, 10 moles/liter sodium hydroxide was added to raise the pH to 11.14. The experiment was performed in a 1000mL beaker with an overhead stirrer. Filtering the slurry; 35.33 g of residue and 118mL of filtrate were collected. Evaporation was noted. The residue was washed with a saturated lithium carbonate solution, filtered and dried. Analysis of the residue showed that 100% cobalt and 82.11% lithium were precipitated as a mixed cobalt and lithium carbonate.
4. Cobalt was precipitated as cobalt hydroxide (test # PTC3-2)
A450 mL solution containing 5.59g/L lithium and 50.01g/L cobalt, pH 1.59, was prepared by: the lithium cobalt oxide is leached with sulfur dioxide in combination with sulfuric acid. The precipitation test was performed by: sodium hydroxide, 10 moles/liter, was added slowly to raise the pH to 10.61 to precipitate the cobalt. The experiment was performed in a 1000mL beaker with an overhead stirrer. Filtering the slurry; 46.48 g of residue and 390mL of filtrate were collected. The residue was washed with deionized water, filtered and dried. Analysis of the residue showed that 100% of the cobalt was selectively precipitated from the lithium and cobalt containing solution as cobalt hydroxide. The final residue contains traces of lithium (about 0.0292%), which can possibly be further purified by additional washing.
5. Precipitating lithium as lithium carbonate (test # PTL 3-2)
The 385mL of solution remaining from the filtrate after test # PTC3-2 above was used for this test. The precipitation test was performed by: 25 grams of sodium carbonate monohydrate (calculated as 1.2 times the stoichiometric amount required to precipitate all of the lithium to lithium carbonate for the solution) was added. The experiment was performed in a 1000mL beaker using an overhead mixer. Filtering the slurry; 7.82g of residue and 318mL of filtrate were collected. The residue was washed with a saturated lithium carbonate solution, filtered and dried. Analysis of the residue showed 53.9% of the lithium was precipitated as lithium carbonate.
6. Generation of dithionate from leached lithium cobalt oxide leached with sulfur dioxide and sulfuric acid
Will be represented by the chemical formula LiCoO2The structured lithium cobalt oxide (Alfa Aesar) was used for this experimental work. A number of leaching experiments were performed by: in the range of 36-50 grams of LiCoO2Mixed with 250mL of sulfuric acid at a concentration ranging from 0.8 mol/l to 1.5 mol/l. Sulphur dioxide gas is continuously bubbled into the leach solution. The final oxidation-reduction potential (ORP) range tested was between 102mV and 401 mV. The leaching vessel consisted of a three-necked round bottom flask and was stirred with a magnetic stir bar. One port of the flask was used to monitor ORP, a condenser was added to the other port to condense the vapor back into the vessel and another port was used to measure temperature. The experiments were performed without temperature control. After 120 minutes of leaching, a sample was taken for analysis of dithionate by ion chromatography. The results are summarized in Table 1.
Table 1.
Test number S2O6 2-(mg/L)
LT 18 27150
LT 19 30294
LT 20 15207
LT 21 23069
LT 22 13290
LT 23 30953
LT 24 19951
LT 25 9260
LT 26 10386
7. Closed cycle test for treating lithium cobalt oxide
Will be represented by the chemical formula LiCoO2The structured lithium cobalt oxide (Alfa Aesar) was used for this experimental work. Lithium cobalt oxide was processed in a closed cycle fashion to simulate the main unit operations in the flow scheme described in embodiment two. The closed cycle test demonstrates the removal of sulfate and dithionate from the following loops: which enables recycling of lithium and water that were not recovered at the end of the flow of the previous cycle to the front end of the flow of the subsequent cycle to be recovered.
The leaching conditions consisted of: the pH is controlled to be about 1.5; 1.2M H in Leaching head (head)2SO4(ii) a 8% pulp density; and SO2Bubbling, and the target ORP is 350 mV. SO at 2 hours for each leaching stage in 4 cycles2After the reductive leach, all the leach head solids visually disappeared.
The leach liquor from the previous leach stage is adjusted to pH 11 by 10M NaOH to precipitate the dissolved cobalt as Co (OH)2. Followed by 2 repulping washing steps and filtration. The wet solid was dried at 60 ℃.
The filtrate from the previous step is then mixed with1.2 times stoichiometric Na relative to lithium concentration measured by ICP2CO3And (4) mixing. The mixed solution was then heated to 95 ℃ for 30 minutes, after which Li was filtered off2CO3And (4) precipitating. The precipitate is saturated with Li at 95 DEG C2CO3And (6) washing. All saturated Li except for closed cycle #12CO3The washing solutions were all by Li generated from previous cycles2CO3And (3) preparing a solid. In the closed cycle, lithium is expected to accumulate in solution, resulting in improved Li recovery. The results from ICP and calculations confirm this conclusion. The calculated lithium recovery for each cycle of the scheme is shown in table 2.
Table 2.
Closed loop numbering % lithium recovery
1 32％
2 36％
3 68％
4 76％
The filtrate from the previous step, which contained a mixture of sodium sulfate, sodium dithionate and unrecovered lithium ion solution, was cooled to 5 ℃ for 2 hours with gentle mixing with an overhead (overhead) mixer to crystallize sodium sulfate decahydrate and sodium dithionate dihydrate. The crystals were collected by filtration and dried at 60 ℃ to collect anhydrous crystals. The weight of dry crystals for cycles 1-4 is shown in Table 3.
Table 3.
Closed loop numbering Weight (g) of dried crystals
1 26.16
2 59.77
3 78.50
4 74.25
An example of a nanofiltration step is described in example 20.
8. Lithium nickel manganese cobalt oxide was leached with sulfur dioxide and sulfuric acid (run # NMC3-5)
Will be represented by the chemical formula LiNi0.33Mn0.33Co0.33O2Structured lithium nickel manganese cobalt oxide (Sigma Aldrich) was used for this experimental work. Leaching is carried out by: 30g of LiNi0.33Mn0.33Co0.33O2Mixed with 255mL of 1.2 mol/l sulfuric acid. Sulfur dioxide gas was continuously bubbled into the leach solution to maintain an oxidation-reduction potential (ORP) of 550 mV. The leaching vessel consisted of a three-necked round-bottomed flask and was fed with a magnetic stir barStirring the mixture. One port of the flask was used to monitor ORP, a condenser was added to the other port to condense the vapor back into the vessel and another port was used to measure temperature. The experiments were performed without temperature control. The leach was determined to be exothermic as the temperature rose to as high as 66 ℃ after 30 minutes of leaching and further cooled to 28 ℃ after 120 minutes of experimentation. Inductively coupled plasma spectroscopy (ICP) analysis of the solution showed that 100% of the lithium, nickel, manganese and cobalt were extracted after 120 minutes of leaching. Analysis by ion chromatography showed that the final leach solution contained 24.1g/L dithionate.
9. Precipitating nickel, manganese and cobalt with NaOH to (Ni, Mn, Co) (OH)2(test # NMC-2-PTC 11)
A200 mL solution containing 7.71g/L lithium, 19.83g/L nickel, 18.09g/L manganese, and 19.38g/L cobalt, pH 0.8 was prepared by: the lithium nickel manganese cobalt oxide is leached with sulfur dioxide in combination with sulfuric acid. The precipitation test was performed by: sodium hydroxide, 10 moles/liter, was slowly added to raise the pH to 10.70 to precipitate nickel, manganese and cobalt. The assay was performed in a 500mL beaker with a magnetic stirrer. The slurry was filtered. 18.70 g of dry residue and 140mL of filtrate were collected. The residue was washed with deionized water, filtered and dried. Analysis of the residue showed that 100% nickel, 100% manganese and 100% cobalt were precipitated as metal hydroxides from the solution containing lithium, nickel, manganese and cobalt. The final residue contains a small amount of lithium (about 0.155%), which can possibly be further purified by additional washing.
10. Precipitation of lithium as lithium carbonate after hydroxide precipitation of nickel, manganese and cobalt with NaOH (run # NMC-2-PTL 11)
The residue from the filtrate after test # NMC-2-PTC-11 was used for this test. The precipitation test was performed by: 14.12 grams of sodium carbonate (calculated as 1.2 times the stoichiometric amount required to precipitate all the lithium to lithium carbonate for the solution) was added. The assay was performed in a 500mL beaker with a magnetic stirrer at 95 ℃ for 15 minutes. Filtering the slurry; 2.39 g of dry residue and 130mL of filtrate were collected. The residue was washed with a saturated lithium carbonate solution, filtered and dried. Analysis of the residue showed that 34.6% of the lithium was precipitated as lithium carbonate.
11. Precipitating nickel, manganese and cobalt as (Ni, Mn, Co) (OH) with LiOH2(test # NMC-2-CT-PTC 3)
A200 mL solution containing 7.30g/L lithium, 18.27g/L nickel, 17.05g/L manganese, and 18.24g/L cobalt, pH 0.66 was prepared by: the lithium nickel manganese cobalt oxide is leached with sulfur dioxide in combination with sulfuric acid. The precipitation test was performed by: 3.34 moles/liter lithium hydroxide was slowly added to raise the pH to 11.07 to precipitate nickel, manganese and cobalt. The assay was performed in a 500mL beaker with a magnetic stirrer. Filtering the slurry; 18.24g of residue and 206mL of filtrate were collected. The residue was washed with deionized water, filtered and dried. Analysis of the residue showed that 100% nickel, 100% manganese and 100% cobalt were precipitated as metal hydroxides from the solution containing lithium, nickel, manganese and cobalt. The final residue contains a small amount of lithium (about 0.787%), which can possibly be further purified by additional washing.
12. Precipitation of lithium to lithium carbonate after hydroxide precipitation of nickel, manganese and cobalt with LiOH (run # NMC-2-CT-PTL 3)
The residue from the filtrate after test # NMC-2-CT-PTC3 was used for this test. The precipitation test was performed by: 27.74 grams of sodium carbonate (calculated as 1.2 times the stoichiometric amount required to precipitate all of the lithium as carbonate for the solution) was added. The assay was performed in a 500mL beaker with a magnetic stirrer at 95 ℃ for 15 minutes. Filtering the slurry; 12.12 grams of dry residue and 184mL of filtrate were collected. The residue was washed with a saturated lithium carbonate solution, filtered and dried. Analysis of the residue showed that 49.8% of the lithium was precipitated as lithium carbonate.
13. Closed cycle test for processing lithium nickel manganese cobalt oxide
Will be represented by the chemical formula LiNi0.33Mn0.33Co0.33O2Structured lithium nickel manganese cobalt oxide (Sigma Aldrich) was used for this experimental work. Processing of lithium nickel manganese cobalt oxide in a closed cycle manner to simulate the description of embodiment threeThe main unit operations in the flow are described. The closed cycle test demonstrates the removal of sulfate and dithionate from the following loops: which enables recycling of lithium and water that were not recovered at the end of the flow of the previous cycle to the front end of the flow of the subsequent cycle to be recovered.
The leaching conditions consisted of: treating a 100g sample, wherein the pH is controlled to about 1.5; 1.5M H in leaching head2SO4(ii) a 10% pulp density; and SO2Bubbling, and the target ORP was 550 mV. SO at 2 hours for each leaching stage in 4 cycles2After the reductive leach, the solids of the leach head visually disappeared.
The leach liquor from the previous leach stage is adjusted to pH 11 by saturated LiOH to precipitate the dissolved nickel, manganese and cobalt as (Ni, Mn, Co) (OH)2. Followed by 2 repulping washing steps and filtration. The wet solid was dried at 60 ℃.
The filtrate from the previous step was then mixed with 1.0 times the stoichiometric amount of Na relative to the lithium concentration measured by ICP2CO3And (4) mixing. The mixed solution was then heated to 95 ℃ for 30 minutes, after which Li was filtered off2CO3And (4) precipitating. The precipitate is saturated with Li at 95 DEG C2CO3And (6) washing. All saturated Li except for closed cycle #12CO3The washing solution is formed by Li generated from the previous cycle2CO3And (3) preparing a solid. In the closed cycle, lithium is expected to accumulate in solution, resulting in improved Li recovery. The results from ICP and calculations confirm this conclusion. The calculated lithium recovery for each cycle of the scheme is shown in table 4.
Table 4.
Closed loop numbering % lithium recovery
1 47％
2 67％
3 78％
4 100％
The filtrate from the previous step, which contained a mixture of sodium sulfate, sodium dithionate and unrecovered lithium ion solution, was cooled to 5 ℃ for 2 hours with gentle stirring using an overhead mixer to crystallize sodium sulfate decahydrate and sodium dithionate dihydrate. The crystals were collected by filtration and dried at 60 ℃ to collect anhydrous crystals. The weight of dry crystals for cycles 1-4 is shown in Table 5.
Table 5.
Closed loop numbering Weight (g) of dried crystals
1 53.22
2 108.29
3 71.75
4 236.11
An example of a nanofiltration step is described in example 20.
14. Lithium nickel cobalt aluminum oxide was leached with sulfur dioxide and sulfuric acid (run # NCA-LT8)
Will be represented by the chemical formula LiNi0.08Co0.15Al0.05O2Structured lithium nickel cobalt aluminum oxide (MTI Corp) was used for this experimental work. Leaching is carried out by: 30g of LiNi0.8Co0.15Al0.05O2Mixed with 245mL of 1.2 mol/l sulfuric acid. Sulfur dioxide gas was continuously bubbled into the leach solution to maintain an oxidation-reduction potential (ORP) of 550 mV. The leaching vessel consisted of a four-port glass reactor and was stirred with an overhead mixer. One port of the flask was used to monitor ORP, a condenser was added to the other port to condense the vapor back into the vessel, another port was used to measure temperature and the last port was used for the overhead mixer. The experiments were performed without temperature control. The leach was determined to be exothermic as the temperature rose to as high as 88 ℃ after 30 minutes of leaching and was further cooled to 50 ℃ after 120 minutes of experimentation. Inductively coupled plasma spectroscopy (ICP) analysis of the solution showed that 100% of the lithium, nickel, cobalt and aluminium were extracted after 120 minutes of leaching. Analysis by ion chromatography showed that the final leach solution contained 11.3g/L dithionate.
15. Precipitating nickel, cobalt and aluminum as (Ni, Co, Al) (OH) with NaOH2(test # NCA-PTC 1)
A200 mL solution, pH 1.06, containing 8.63g/L lithium, 57.82g/L nickel, 10.54g/L cobalt, and 1.17g/L aluminum was prepared by: the lithium nickel cobalt aluminum oxide is leached with sulfur dioxide in combination with sulfuric acid. The precipitation test was performed by: sodium hydroxide, 10 moles/liter, was slowly added to raise the pH to 11.09 to precipitate nickel, cobalt and aluminum. The assay was performed in a 500mL beaker with a magnetic stirrer. The slurry was filtered. 27.15 g of dry residue and 135mL of filtrate were collected. The residue was washed with deionized water, filtered and dried. Analysis of the residue showed that 100% nickel, 100% manganese and 100% cobalt were precipitated as metal hydroxides from the solution containing lithium, nickel, manganese and cobalt. The final residue contains a small amount of lithium (about 0.078%), which can possibly be further purified by additional washing.
16. Precipitation of lithium as lithium carbonate after hydroxide precipitation of nickel, cobalt and aluminum with NaOH (test # NCA-PTL 1)
The residue from the filtrate after test # NCA-PTL 1 was used for this test. The precipitation test was performed by: 15.82 grams of sodium carbonate (calculated as 1.2 times the stoichiometric amount required to precipitate all of the lithium as carbonate for the solution) was added. The assay was performed in a 500mL beaker with a magnetic stirrer at 95 ℃ for 15 minutes. Filtering the slurry; 2.88 g of dry residue and 125mL of filtrate were collected. The residue was washed with a saturated lithium carbonate solution, filtered and dried. Analysis of the residue showed that 31.5% of lithium was precipitated as lithium carbonate.
17. Precipitating nickel, cobalt and aluminum as (Ni, Co, Al) (OH) with LiOH2(test # NCA-CT-PTC 2)
A200 mL solution containing 6.64g/L lithium, 46.84g/L nickel, 8.45g/L cobalt, and 0.89g/L aluminum, pH 0.35 was prepared by: the lithium nickel cobalt aluminum oxide is leached with sulfur dioxide in combination with sulfuric acid. The precipitation test was performed by: 4.44 moles/liter lithium hydroxide was added slowly to raise the pH to 11.03 to precipitate nickel, cobalt and aluminum. The assay was performed in a 500mL beaker with a magnetic stirrer. Filtering the slurry; 18.55 g of residue and 202mL of filtrate were collected. The residue was washed with deionized water, filtered and dried. Analysis of the residue showed that 100% nickel, 100% cobalt and 100% aluminum were precipitated as metal hydroxides from the solution containing lithium, nickel, cobalt and aluminum. The final residue contains a small amount of lithium (about 0.648%), which can possibly be further purified by additional washing. 18. Precipitation of lithium to lithium carbonate after hydroxide precipitation of nickel, cobalt and aluminum with LiOH (run # NCA-CT-PTL 2)
The remainder from the filtrate after test # NCA-CT-PTC 2 was used for this test. The precipitation test was performed by: 27.31 grams of sodium carbonate (calculated as 1.0 times the stoichiometric amount required to precipitate all of the lithium as carbonate for the solution) was added. The assay was performed in a 500mL beaker with a magnetic stirrer at 95 ℃ for 15 minutes. Filtering the slurry; 14.04 g of dry residue and 185mL of filtrate were collected. The residue was washed with a saturated lithium carbonate solution, filtered and dried. Analysis of the residue showed that 55.97% of the lithium was precipitated as lithium carbonate.
19. Closed cycle test for treatment of lithium nickel cobalt aluminum oxide
Will be represented by the chemical formula LiNi0.8Co0.15Al0.05O2Structured lithium nickel cobalt aluminum oxide (MTI Corp) was used for this experimental work. The lithium nickel cobalt aluminum oxide was processed in a closed cycle fashion to simulate the main unit operations in the flow scheme described in embodiment three. The closed cycle test demonstrates the removal of sulfate and dithionate from the following loops: which enables recycling of lithium and water that were not recovered at the end of the flow of the previous cycle to the front end of the flow of the subsequent cycle to be recovered.
The leaching consisted of: treating a 400g sample, wherein the pH is controlled to about 1.5; 1.2M H in the leaching head2SO4(ii) a 10% pulp density; and SO2Bubbling, and the target ORP was 550 mV. SO at 2 hours for each leaching stage in 7 cycles2After the reductive leach, the solids of the leach head visually disappeared.
The leach liquor from the previous leach stage is adjusted to pH 10.5 by saturated LiOH to precipitate the dissolved nickel, cobalt and aluminium as (Ni, Co, Al) (OH)2. Followed by 2 repulping washing steps and filtration. The wet solid was dried at 60 ℃.
The filtrate from the previous step was then mixed with 1.2 times the stoichiometric amount of Na relative to the lithium concentration measured by ICP2CO3And (4) mixing. The mixed solution was then heated to 95 ℃ for 30 minutesClock, then filter Li2CO3And (4) precipitating. The precipitate is saturated with Li at 95 DEG C2CO3And (6) washing. All saturated Li except for closed cycle #12CO3The washing solutions were all by Li generated from previous cycles2CO3And (3) preparing a solid. In the closed cycle, lithium is expected to accumulate in solution, resulting in improved Li recovery. The results from ICP and calculations confirm this conclusion. The calculated lithium recovery for each cycle of the scheme is shown in table 6.
Table 6.
Closed loop numbering % lithium recovery
1 51％
2 62％
3 69％
4 70％
5 80％
6 86％
7 100％
The filtrate from the previous step, which contained a mixture of sodium sulfate, sodium dithionate and unrecovered lithium ion solution, was cooled to 5 ℃ for 2 hours with gentle mixing with an overhead mixer to crystallize sodium sulfate decahydrate and sodium dithionate dihydrate. The crystals were collected by filtration and dried at 60 ℃ to collect anhydrous crystals. The weight of dry crystals for cycles 1-4 is shown in Table 7.
Table 7.
Closed loop numbering Weight (g) of dried crystals
1 67.9
2 185.3
3 161.4
4 175.0
5 218.7
6 109.3
7 205.6
An example of a nanofiltration step is described in example 20.
20. Nanofiltration
Nanofiltration tests were performed by: a feed solution containing 32.23g/L sulphate and 24.0g/L dithionate was pumped through a Dow Filmtec NF270-400 nanofiltration membrane. The feed flow rate was set to 5.65L/min. The pressure at the inlet of the membrane was measured to be 29.1 bar. The pressure at the concentrate outlet was measured to be 28.5 bar. The permeate flow rate through the membrane was measured to be 0.65L/min. A sample of the permeate was collected and found to have a sulfate of 2.30g/L and dithionate of 2.84g/L by ion chromatography. The concentrate flow rate was calculated to be 5.0L/min. The concentrate was calculated to contain 36.13g/L sulfate and 26.80g/L dithionate. The sulphate rejection (rejection) was calculated to be 92.2% and the dithionate rejection was calculated to be 85.5%.
Although the preferred embodiments of the present invention have been disclosed for illustrative purposes, it should be understood that various changes, modifications and substitutions may be incorporated in the embodiments without departing from the spirit of the invention, which is defined by the claims which follow.

Claims (18)

1. A process for water removal and/or recycling from liquor comprising sodium sulphate and/or sodium dithionate resulting from processing of a cobalt resource material substantially free of lithium, comprising the steps of:
a. precipitating cobalt, in whole or in part, as cobalt carbonate, after which it is removed, in whole or in part, from the liquor by centrifugation or filtration;
b. crystallizing sodium sulfate and sodium dithionate to separate a majority of the sodium sulfate and sodium dithionate from the solution;
c. removing the sodium sulfate and sodium dithionate crystals;
d. heating the sodium sulfate and sodium dithionate crystals to form anhydrous sodium sulfate, sulfur dioxide, and water; and
e. the anhydrous sodium sulfate was separated.
2. The process of claim 1 wherein said water formed in step d is formed in the form of steam.
3. A process for water removal and/or recycling from liquor comprising sodium sulphate and/or sodium dithionate resulting from processing of a cobalt resource material comprising lithium, comprising the steps of:
a. precipitating cobalt, in whole or in part, as cobalt carbonate and lithium, in whole or in part, as lithium carbonate, after which they are removed, in whole or in part, from the liquor by centrifugation or filtration;
b. crystallizing sodium sulfate and sodium dithionate to separate a majority of the sodium sulfate and sodium dithionate from the solution;
c. removing the sodium sulfate and sodium dithionate crystals; and
d. heating the sodium sulfate and sodium dithionate crystals to form anhydrous sodium sulfate, sulfur dioxide, and water; and
e. the anhydrous sodium sulfate was separated.
4. The process of claim 3 wherein said water formed in step d is formed in the form of steam.
5. The process of claim 3, comprising the presence of manganese in the process.
6. The process of claim 5 wherein the manganese is recovered as manganese carbonate.
7. The process of claim 3, including the presence of nickel in the process.
8. The process of claim 7, wherein the nickel is recovered as nickel carbonate.
9. The process of claim 3, wherein the cobalt resource material comprises a lithium ion battery positive electrode material.
10. A process for water removal and/or recycling from liquor comprising sodium sulphate and/or sodium dithionate resulting from processing of a cobalt resource material substantially free of lithium, comprising the steps of:
a. precipitating cobalt, in whole or in part, as cobalt hydroxide, after which it is removed, in whole or in part, from the liquor by centrifugation or filtration;
b. crystallizing sodium sulfate and sodium dithionate to separate a majority of the sodium sulfate and sodium dithionate from the solution;
c. removing the sodium sulfate and sodium dithionate crystals;
d. heating the sodium sulfate and sodium dithionate crystals to form anhydrous sodium sulfate, sulfur dioxide, and water; and
e. the anhydrous sodium sulfate was separated.
11. The process of claim 10 wherein said water formed in step d is formed in the form of steam.
12. A process for water removal and/or recycling from liquor comprising sodium sulphate and/or sodium dithionate resulting from processing of a cobalt resource material comprising lithium, comprising the steps of:
a. precipitating cobalt, in whole or in part, as cobalt hydroxide, after which it is removed, in whole or in part, from the liquor by centrifugation or filtration;
b. precipitating lithium, wholly or partially, from the cobalt hydroxide depleted liquor of step a as lithium carbonate, after which it is removed wholly or partially from said liquor by centrifugation;
c. crystallizing sodium sulfate and sodium dithionate to separate a majority of the sodium sulfate and sodium dithionate from the solution;
d. heating the sodium sulfate and sodium dithionate crystals to form anhydrous sodium sulfate, sulfur dioxide, and water; and
e. the anhydrous sodium sulfate was separated.
13. The process of claim 12, comprising the presence of manganese in the process.
14. The process of claim 13, wherein the manganese is recovered as manganese hydroxide.
15. The process of claim 12, including the presence of nickel in the process.
16. The process of claim 15, wherein the nickel is recovered as nickel hydroxide.
17. The process of claim 12, wherein the cobalt resource material comprises a lithium ion battery positive electrode material.
18. The process of claim 12 wherein said water formed in step d is formed in the form of steam.
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Families Citing this family (12)

* Cited by examiner, † Cited by third party
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US10308523B1 (en) * 2017-11-07 2019-06-04 Rocher Manganese, Inc. Processing of cobaltous sulphate/dithionate liquors derived from cobalt resource
US11142466B2 (en) * 2017-11-22 2021-10-12 Nemaska Lithium Inc. Processes for preparing hydroxides and oxides of various metals and derivatives thereof
CN109734107A (en) * 2018-12-28 2019-05-10 池州西恩新材料科技有限公司 A kind of resource recycle method of the useless positive electrode of lithium battery
CN111092273B (en) * 2019-09-14 2022-11-18 湖南金源新材料股份有限公司 Novel method for comprehensively recovering cobalt, nickel, manganese and lithium elements from ternary battery waste
KR102205442B1 (en) * 2020-05-26 2021-01-20 주식회사 에코프로이노베이션 Method for recovering valuable metals using lithium carbonate from waste electrode materials of lithium-ion batteries
US11811035B2 (en) 2020-05-27 2023-11-07 Ut-Battelle, Llc Recovery of critical elements from end-of-life lithium ion batteries with supported membrane solvent extraction
US11316208B2 (en) 2020-07-08 2022-04-26 American Hyperform, Inc. Process for recycling cobalt and nickel from lithium ion batteries
CN112642837A (en) * 2020-12-02 2021-04-13 攀钢集团研究院有限公司 Resource utilization method of SDS (sodium dodecyl sulfate) desulfurization waste residues
US11302961B1 (en) 2021-06-30 2022-04-12 Storagenergy Technologies, Inc. Semi-solid polymer electrolyte and uses thereof in electrochemical devices
US11909016B2 (en) 2021-08-24 2024-02-20 American Hyperform, Inc. Recycling process for isolating and recovering rare earth metals and nickel hydroxide from nickel metal hydride batteries
US11932554B2 (en) 2022-04-11 2024-03-19 American Hyperform, Inc. Method of recovering high nickel content cathode material from recycled lithium ion and nickel metal hydride batteries
EP4328335A1 (en) * 2022-08-26 2024-02-28 H.C. Starck Tungsten GmbH Method for the production of cathode material from battery waste

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3994716A (en) * 1973-03-30 1976-11-30 Sherritt Gordon Mines Limited Process for the production of finely divided cobalt powders
US4186176A (en) * 1977-08-04 1980-01-29 Asahi Kasei Kogyo Kabushiki Kaisha Method of simultaneously removing sulfur dioxide and nitrogen oxides from exhaust gases
CN1973399A (en) * 2004-06-21 2007-05-30 丰田自动车株式会社 Method of disposing of lithium battery
CN102476887A (en) * 2010-11-29 2012-05-30 攀钢集团钢铁钒钛股份有限公司 Treatment method of vanadium recovery wastewater
CN103168109A (en) * 2010-08-18 2013-06-19 美国锰业股份有限公司 Processing of manganous sulphate/dithionate liquors

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3425206B2 (en) * 1994-01-20 2003-07-14 住友金属鉱山株式会社 Method for recovering valuable resources from used lithium secondary batteries
JP3452769B2 (en) * 1997-09-18 2003-09-29 株式会社東芝 Battery treatment method
JP4144820B2 (en) * 1998-06-30 2008-09-03 株式会社東芝 Method for regenerating positive electrode active material from lithium ion secondary battery
TW511306B (en) 2001-08-20 2002-11-21 Ind Tech Res Inst Clean process of recovering metals from waste lithium ion batteries
CN1274602C (en) * 2003-11-18 2006-09-13 深圳市格林美高新技术有限公司 Cobaltosic oxide preparation method for lithium ion battery
JP4746853B2 (en) * 2004-07-12 2011-08-10 和光 加藤 High purity metal hydroxide, purification method and production method thereof, hydroxide and oxide obtained by these methods, and synthetic resin composition and synthetic resin molded article
CN102947225A (en) 2010-02-17 2013-02-27 辛博尔股份有限公司 Processes for preparing highly pure lithium carbonate and other highly pure lithium containing compounds
JP2013194315A (en) * 2012-03-22 2013-09-30 Dowa Eco-System Co Ltd Method for recovering valuable material from lithium ion secondary battery
CN102820468B (en) * 2012-09-11 2014-11-05 赣州腾远钴业有限公司 Preparation process of cobaltosic oxide for continuous production of batteries
JP5706457B2 (en) * 2013-02-27 2015-04-22 Jx日鉱日石金属株式会社 Method for separating and recovering metal from mixed metal solution

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3994716A (en) * 1973-03-30 1976-11-30 Sherritt Gordon Mines Limited Process for the production of finely divided cobalt powders
US4186176A (en) * 1977-08-04 1980-01-29 Asahi Kasei Kogyo Kabushiki Kaisha Method of simultaneously removing sulfur dioxide and nitrogen oxides from exhaust gases
CN1973399A (en) * 2004-06-21 2007-05-30 丰田自动车株式会社 Method of disposing of lithium battery
CN103168109A (en) * 2010-08-18 2013-06-19 美国锰业股份有限公司 Processing of manganous sulphate/dithionate liquors
CN102476887A (en) * 2010-11-29 2012-05-30 攀钢集团钢铁钒钛股份有限公司 Treatment method of vanadium recovery wastewater

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